Condensation of aldehydes with triazinyl aryl sulfonic acid derivatives and process of preparing same



United States Patent CONDENSATION 0F ALDEHYDES WITH TRIAZ- INYL ARYL SULFONIC ACID DERIVATIVES AND PROCESS OF PREPARING SAME Gaetano F. DAlelio, South Bend, Ind., assignor, by direct "and 'mesiie assignments, to Dell Mon Research (30., Cleveland Ohio a corporation of Delaware No Drawing. Filed Dec. 5, 1958, Ser. No. 778,290

16 Claims. (Cl. Ell -45.2)

,Inthe above formula, n and m areintegers of at least one and no more than two, andthe sum of m and ndoes not exceed three; A represents an aldehyde-readable group; T represents an aryl sulfonic acid group; andeY "represents any monovalent radical. In the above formula, it maybe seenthat when n is one, m can be one with one I group, or m can be two with no T group; orifn is two then m is one and there will be no Y group; and when Y is one then m and 11 must each be one. The only requirementin this invention for the triazine derivative is thatit have atleastone aldehyde reactable group A, and atleast one T group. For purposes of simplicity, the trivalent vl,3,5,-triazine vor symmetrical triazine nucleus is sometimes represented hereinafter by C N T he aldehyde-reactable group, is a grouping ofatoms .or radicals that react with aldheyde or polymeric-aldehydes to form a derivative such as illustratedby the folon on o As illustrative examples of the aldehyde-reactable group, A,Hthere' areernentionedythe;following groups:

ll x-CNHR, as disclosed in my ILS. Patent 2,295,562, i ssu cl ptember 15, 1942, wherein x is an integer of atleastl and not more than 2,Y represents a member oi'thefcliass consistingoicxygen and sulfur, and R represents a member of the class consist ng of hydrogen an d monovalent hydrocarbon and halohydrocarbon radicals;

NR-NR )-NHR, as disclosed in my U,S. Patent 2,295,565, issued September 15, 1942, wherein Y represents a member of the class consistin g of hydrogen and monovalent hydrocarbon and halohydrocarbon radicals;

I l -NR (J-NHR, as disclosed in my U.S. Patent 2,312,688, issued March 2, 1943, wherein Y representsa member of the class consisting of oxygen and sulfur and R represents a member of the class consisting of hydrogen and hydrocarbon radicals and halohydrocarbon radicals; a -V 11:"

Z l SO,,Rr,.'( JNR-Y-SO NHR, as disclosed in my U.S. Patent 2,312,690, issued March 2, 1943, wherein n represents an integer and isat least one and not more than 2, Z representsamember of the class consisting 01 oxygen and sulfur,'Y represents'a bivalent carbocyclic radical, and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon radicals and substituted hydrocarbon radicals; g 3:: 7 1 Y a NRZSO NHR, as disclosed in my U.S. Patent 2,312,697, issued March 2, 1943, wherein Z'represents an aryl nucleus and;R'-'represents a member of the class consisting of hydrogen and monovalenthydrocarbon radicals and substituted hydrocarbon radicals; I i

issued March 2, 1943, wherein n represents'an integer and is at least one and not'more than 2, Z represents a member-oi the class consisting of oxygenaud sulfur, Y represents a divalentcarbocyclic radical and .R represents a member of the class consisting of hydrogen and monovalent hydrocarbon radicalsand substitutedhydrocarbon radicals;

NHR, as disclosed in my U.S. Patent 2,335,846, issued December 7, 1943, wherein R represents a member of the class consisting of hydrogen and monovalent'hydrocarbon radicals and halohydrocarbonradicals;

ZOON HR, wherein Z represents a divalcnt hydrocarbon radical and R represents hydrogen and a monovalent hydrocarbon radical and substitutedhydrocarbon-radicals;

BZOON HR, wherein B represents a member of the class consisting l of oxygen, sulfur and -NR, Z represents a divalent hydrocarbon radical and substituted hydrocarbon radicals, and Rrepresents a member-of the class of hydrogen and monovalent'hydrocarbonradicals and substituted hydrocarbon radicals; ,1 i

HNRNR, wherein R represents a member of the class consisting of hydrocarbon radicals;

HO--Z, wherein Z represents a divalent aromatic radical and substituted hydrocarbon radicals as hereinabove defined... A iew typical I. triazine compounds are (H0 0 11,) (Q N;)[ P R t hydrogen and monovalcnt hydrocarbon radicals and substituted HOZNR-, whereinR represents hydrogen and monovalent hydrocarbon radicals and substituted hydrocarbon radicals, and Z represents a divalent aromatic radical and substituted hydrocarbon radicals as hereinabove described.- A few typical compounds are hydrocarbon radical-and subst uted hydrocarbon radicals as pre- RzN CYNR-CHR', as disclosed in my US. Patent 2,339,623, issued January 18, 1944', wherein Y represents oxygen or sulfur, at least one B. represents hydrogen and the other Bs represent hydrogen, a

-monoval'ent hydrocarbon radical or a monovalentzhalogenated hydrocarbon radical, and R represents hydrogen or a monovalent aliphatic, carbocyclic or aromatic hydrocarbon radicalof not'more' than o'carbon P'FQPFSWW a z Thus it may be seen that A may be any aldehyde-resemble group.

In the above triazirie derivativeformulaflycah be R which represents hy'drogenor anymonovalent'i'hydrocairhon radical, whether saturated or unsaturated, substituted halogens,as, for example,fluorin fchloi ine;niti'ofgroiips, 'nitr'os o groups, amino groups, carboxy groups, carb i groups; 'methoxy and 'aryloxy groups, mercap'to lgroups, etcL; Y can also be hydroxyl and the alkoxyf afidfar cyclic hydroxy compounds;suchiasfrnethyl' 1c 0 radicals of aliphatic, cycloaliphatic, aromatic andfhetefo alcohol, butyl alcohol, isobutyl alcohol, dodecyl alcohol, phenol, the m-, and p-cresols, the xylenols, the naphthols, ethylene glycol, methyl glycol ether, butyl glycol ether, glycerine, pentaerythritol, naphthol, hydroxy pyridine, including the alkoxy and aryloxy radicals of hydroxy acids and esters such as lactic acid, ethyl lactate, allyl lactate, methyl salicylate, and the chloro derivatives such as chlorophenol, chloronaphthol, ethylene chlorohydrin, and the acetoxy derivatives such as acetoxyethyl alcohol, etc., and these radicals are represented by RO--; Y can also be RS groups which are the mercapto equivalents to RO--; Y can also be NR that is, an amino group, a monosubstituted amino group or a disubstituted amino group, as for example, the radicals of methylamine, ethylamine, butylamine, nonylamine, benzyl amine, dimethyl amine, aniline, naphthylarnine, etha nolamine, diethanolamine, diisopnopylamine, methyl- =aniline, piperidine, aminopyridine, and the hydrazine radicals, namely, R NNR- from hydrazine, unsymmetrical dimethyl hydrazine, symmetrical dimethyl hydrazine, trimethyl hydrazine, phenyl hydrazine; Y can also be the N-radicals of the amino-acids, the aminoesters, the amino-amides, and the amino-nitriles, specific examples of which are NHC2B4CN, NHCsHrNHOCCH Y can also be radicals of alkylene imines, such as, for example,

GHQ-CH1, CH;CH-CH2, CHgOH-OH-GH canton-4m,

N N N l I and the radicals of malonic esters and substituted malonic esters, nitriles, and amides, such as, for example,

CH(CN) CH[CON(CH COO CH COOCzHs C O-CHa CN COOCzHa etc.; or Y can be the radical of another triazinyl ring, e.g., (CH3NH)2(C3N3)-, (HO)2(C3N3)-, DI the triazine ring can be attached through a bridge, such as carbon, selenium, etc., such as, for example,

resents a member of the class consisting of hydrogen,

monovalent hydrocarbon radicals and substituted hydrocarbon radicals, as previously described, Z represents a member of the class consisting of polyvalent aromatic hydrocarbon radicals and substituted aromatic hydrocarbon radicals, p represents a numerical value of one' to three, and q a value of zero to six. These groups can be represented by the structure (-B),-Z-(SO H),, wherein B represents -O(CR NR(CR --NR--NR, etc., r represents a value of 0 or 1, and p, q, and R are as previously defined, and (CR can also be a cycloaliphatic group.

Thus, alternately the triazine derivatives used in the practice of this invention are described by the formula (A) m N N wherein A, Y, B, Z, m, n, p, and r have the meaning hereinabove given. The S0 H group represents not only the free acid but also its salts, such as the sodium, potassium, lithium, calcium, copper, chromium, ammonium, amine salts (e.g. ethanol amine, diethanol amine, isopropanol amine, polyethylene amine, aminophenol, etc.), hydrazine, protein, etc.

Illustrative examples of polyvalent aromatic radicals that Z represents in the above formula are phenylene, xenylene, naphthylene, etc.; the corresponding trivalent and tetravalent radicals, polyvalent aliphatic-substituted aromatic, e.g., 2,4-tolylene, ethyl-2,5-phenylene, isopropyl- 3,4 phenylene, 1 butyl 2,4 naphthylene, diphenylene, phenoxyphenylene, phenoxynaphthylene, ethyl phenylene, etc., and their homologues, as well as those polyvalent radicals with one or more of their hydrogen atoms replaced by a substituent, e.g., acyl, alkyl sulfamyl, alkenyl hydroxy, cyano, alkoxy, aryloxyl, a COOR group, etc. Specific examples of substituted polyvalent radicals that Z represents are chlorophenylene, chloronaphthylene, bromophenylene, chloroxenylene, chlorotolylene, ethoxyphenylene, acetophenylene, sulfamylphenylene, acetoxyphenylene, hydroxyphenylene, phenoxyphenylene, methylphenylene, allylphenylene, etc. Preferably Z represents a phenylene or a naphthylene radical, or the corersponding trivalent and tetravalent radicals.

In practicing this invention the initial condensation reaction can be carried out at normal or elevated temperatures, at atmospheric, subatmospheric, or super-atmospheric pressures, and under natural, alkaline, or acid conditions. Preferably, in most cases, the reaction between the components is initiated under alkaline conditions.

Any substance yielding an alkaline or an acid aqueous solution can be used in obtaining alkaline or acid conditions for the initial condensation reaction. For example, an alkaline substance such as soduim, potassium carbonate, mono-, di-, or tri-amines, etc., can be used. In some cases, it is desirable to cause the initial condensation reaction between the components to take place in the presence of a primary condensation catalyst and a secondary condensation catalyst. The primary catalyst can be either an aldehyde-non-reactable nitrogen-containing basic tertiary compounds, e.g., tertiary amines such as trialkyl (e.g. trimethyl, triethyl, etc.) amines, or an aldehyde-reactable nitrogen-containing basic compound, for instance, ammonia, primary amines (e.g. ethyl-amine, propyl amine, etc.) and secondary amines (e.g. dipropylamine, dibutylamine, etc.) The secondary condensation catalyst, which ordinarily is used in an amount less than the amount of the primary catalyst, advantageously is a fixed alkali, for instance, a carbonate, cyanide, or hydroxide of an alkali metal (e.g. sodium, potassium, lithium, etc.)

Illustrative examples of acid condensation catalysts that can be employed are inorganic or organic acids, such as hydrochloric, sulfuric, phosphoric, acetic, lactic, acrylic,

( Hun-0 ace-snar malonic, etc or acid salts, such as sodium acid sulfate, monosodium phosphate, monosodium phthalate, etc. Mixtures of acids, ,of acid salts, or acids and acidsalts can be employed, if desired. The reaction between the aldehyde, e.g., formaldehyde, :and the triazine derivative can be carried out in the presence of solvents, diluents, fillers, or other natural or synthetic resinous bodies, or while admixed with other materials that also can react with the aldehydic compound or :with the triazine derivative, e.g., ketones, urea, thiourea, selenourea, iminourea (guanidine), substituted ureas, .thioureas, selenoureas, and iminoureas, numerous examples of which are given in my U .S. Patent 2,322,56 6, issued June 22, ;1943;.monoamides of monocarboxylic acids and :polycarboxylicacids and polyamides of polycarbox- -ylic acid, e.g., acetamide, halogenated acetamides (e.g. chloroacetamide), maleic monoamide, malonic monoamide, phthalic monoamide, maleic diamide, fumaric diaide, malonic diamide, itaconic diamide, succinic diamide, phthalic diamide,.the monoamide, diamide and triamide of tricarballylic acid, etc.; aldehyde-reactable diazines compounds, such as are disclosed in my US. Patent 382,211, issued August 14, 1945; aminotriazines, e.g., melamine, ammeline, ,ammelide, melem, melam, melon, etc.; phenol and. substituted phenols, e.g., the cresols, the .xylenols, the tertiary alkyl-phenols and other phenols, :such as mentioned in my U.S.,Patent 2,339,441; monohy- .rdricand polyhydric alcohols, e.g., butylpropylene glycol, rpentaerythritol, polyvinyl alcohol,etc.; amines, including .aromaticamines, e.g., aniline, etc. and the like. In such .;oases, the triazine derivative should represent 5-95 by weight of jthealdehyde reactiveportion of such mixture. The modifying reactants can be incorporated with the triazine derivative andthe aldehyde to form-an intercon- -densationproduct.by mixing'all the reactants and efiect- .ing condensation therebetween or by.various permutations ofreactants. For instance, a partial condensation product can be formed of ingredients comprising (1). urea or melamine or urea and melamine, (2) a triazine derivative of this invention, (3) an aldehyde, including polymeric aldehydes, hydroxy aldehydes and aldehyde-addi-,

Some of the condensation products of this invention are thermoplastic materials even at an advanced stage of condensation, while others are thermosetting or potentially thermosetting bodies that a convert "under heat. or .nnder heat and pressureto aninsoluble infusible state. ,The thermoplastic --condensation products are -of particular value as plasticizers for other synthetic resins. The thermosetting, or potentially thermosetting resinuous condensation products, alone or mixed with fillers, pigments, dyes, lubricants, plasticizers, curing agents, etc., can be used, for example, in the production of molding and laminating compositions. In other. cases, they, can be used as ion exchange resins and as tanning agents.

The liquid intermediate condensation products of this invention can be concentrated: by the removal or, or diluted further by the addition of, volatile solvents, to form liquid coating compositions of adjusted viscosity and concentration. The heat-convertible or potentially heat-convertible resinous condensation products, can be used in the liquid state, for instance, as impregnantsfor wood, leather, paper and other porous bodies; assurface-coating materials in the production of paints, varnishes, lacquers, enamels, etc.; for generalvadhesive, applications in producing laminated articles, and ,for. other purposes. The liquid, heat-hardenable or potentially heat-hardenable condensation products also can be used directly as casting resins, while those which are of gel-like nature'in the partially condensed state can be granulated and dried to form clear, unfilled heat-convertible resinous products.

- Illustrative examples of aldehyde-addition products that can be used instead of the aldehydes them'selvesare the mono-and poly- (N-carbinol) derivatives, particularly the ,monoand polymethylol derivatives of 'urea, thiourea, selenurea, and iminourea, and substitutedureas, thioureas, selenoureas, and iminoureas, monoand .poly-(N-ear .binol) derivatiyesof amides orpolycarboxylic acids, e.g., maleic,,itaconic, fumaric, adipic, malonic, su ccinic, citric, phthalic, etc., monoand poly-(N-carbinol) derivatives o theam not ia ol s ,mo oa d po -tN- bi n ,rivatives of the aminotriazines. Particularly good results are obtained with active methylene-containing bodies as am ethylol urea, more particularly mono anddimethyl ol 'nreas a methylol aminotriazine, more particularly a methylol melamine, e.g., monomethylol melamine and polyrnethylol melamines (di-, tri-, tetra-, penta and hexamethyiol melamines). Mixtures of aldehydes and aldehyde-addition products canbe employed, e,g., mixtures of formaldehyde and methylol compounds, such, for instance, as dimethylol urea, trimethylol melamine, hexamethylol melamine, etc.

The ratio of the aldehydic reactant to the triazine de rivative can be varied over a wide range depending upon the particular properties desired in the finished product. Ordinarily these reactants are employed in an amount corresponding to at-least one mole of the aldehyde, especially formaldehyde, for each mole ofthetriazine derivative. -:Thus, for example, onetoseven or eight or more moles of analdehyde canbe used for each inole of the 'triazine derivative. =When'an aldehyde is available for reaction in the formof an alkylol derivative, more par- .ticularly a methylol derivative such, for instance, as di- -.-methylol urea, trimethylol melamine, .etc., then'higher amounts of such aldehyde additi'on,productsare used, for instance, from 2 to 3 up to 15 to 20 or more moles of such alkylol derivatives for each mole of the triazine der va As indicated hereinbefore, the properties of the fundarnental resincan bevaried wideiyjqy introducing other ether, etc.;, amides, such as formarnide, stearamide, acryl- V amide, benzene sulfonamides, toluene sulfonamide, the aryl disulfonamides, adipic diamide, phthalamide, etc.; amines, e.g., ethylene diamine,.phenylene diamine, etc.;

lgetones, ineluding halogenated ketones, etc.; nitriles, in-

cluding halogenated nitriles, e.g., acrylonitrile, methacrylonitrilc, succinonitrile, fumaryl 'nitrile, chloroacetonitr-iles, etc.; acylated ureas, more particularly halogenated acylatedureas of the kind described in my U.S. Patent 2,851,559, and others. a

' The modifying bodies also can take the form of high molecular weight bodies with or without resinous characteristics,- for example, hydrolyzed wood products, forcondensation products, aminotriazine, aldehyde condensation products, aminotriazole-aldehyde condensation products, polyacrylamide, styrene-maleic imide copolymers, etc. Other examples of modifying bodies are the ureaaldehyde condensation products, the aniline-aldehyde condensation products, furfural condensation products, phenol-aldehyde condensation products, modified or unmodified, saturated or unsaturated polyhydric-alcoholpolycarboxylic acid condensation products, water-soluble cellulose derivatives, natural gums and resins, such as shellac, rosin, etc.; polyvinyl compounds, such as polyvinyl esters, e.g., polyvinyl acetate, polyvinyl butyrate, etc., polyvinyl ethers including polyvinyl acetals, especially polyvinyl formal, etc.

Dyes, pigments, plasticizers, mold lubricants, opacifiers, various reinforcing fillers, such as very finely ground clays, silica (e.g. Aerosil) wood flour, ground glass, mica, etc., can be compounded in accordance with conventional practice to provide various thermoplastic and thermosetting compositions.

The modified and unmodified condensation products have a wide variety of uses. They can be used as ion exchange resins in the conventional manner, or their copper or 8-hydroxyquinoline salts as wood preservatives, or as fertilizer additives, as for example, in the form of their iron or manganese salts, or as an additive to paper to increase its wet strength, or the calcium zinc, magnesium salts, etc., as molding compounds whereby they can also be used as modifiers for other natural and synthetic polymers, as for example, laminating varnishes in the production of laminated articles wherein sheet materials, e.g., paper, cloth, sheet asbestos, glass mats, and glass fibers, etc., are coated and impregnated with resin, super- Preferably, the tannage should be very pale or waterwhite in color. These objectives are readily achieved by the products of this invention. For example, the tolerance to salt solution, that is, the salting out value and the water solubility of the condensation products can be modified by varying the number of aryl sulfonic groups attached to the triazine ring, e.g.

or (NH (C N )(NHC H SO Na), or by cocendensing with urea, melamine, dimethylol urea, dimethylol melamine, trimethylol melamine, phenol alcohols, etc., and by varying the ratio of such modifying cocondensing substances. Also, in accordance with the practice of this invention, the fat liquoring characteristic of the tannage can be readily modified by changing the values of R in the triazine derivative, for example, by using and NH C N (NHC H SO H) Furthermore, the solubility or dispersibility of the condensation product can be increased by using as Y groups, those groups that increase solubility, such as H(OCH CH ),,O where n has a numerical value from one to 50 or more. Also, the tanning compounds of this invention can also be modified so that they are act as preservatives, not only for leather but for such substances as wool, cotton, wood, paper, etc., by introducing into the triazine nucleus such groups as -.NIlC H AsO I-l --NHC H As=O, NHC H AsCl,, etc.

Among the triazine derivatives embraced by the formulas of the various classes of compounds used in producing the new condensation products of this invention are the triazines having the substituents indicated by the groups attached to the structure of electrical resistors, etc. A The condensation products of this invention are particu- 6 larly useful in the treating and tanning of leathers. As is well known, resin tannage must be water-soluble or water f f dispersible and their solutions should tolerate a fair concentration of salt; they should be capable of penetrating into the skin before and during early stages of tanning and before and during the early stages of polymerization. in the following table.

Substltuent A Substituent Y Substltuent T -NH: -NH2 NHC5H4SO3H NH: NHCH4SO3H "NHCuH4SO3H r 'NH: NHCzHu -N*C5H4SO3H -NHC5H5 NH3 -NHNHC&H4SO3H NHOH: --NHCH; 'OC6H4SO3H -NH: Cl NHCQ.H4SOZH --NH;| OH -NHCaHa(SO.-4H),

nmoooms- NBt00oHPs -NHCaHa(CHa)(SO,-,H)

NH2CON'HNH- NHgO0NHN'H- -NHO6H4SO3H HOOJLNH- HOCsH4NH- -00H:(S03H)(0H=) HOC5H4S HOC5HANH -OC6H3(G1)(SO3H) NHlGOmL- HOC6H4s' OOQH4COHASOBH HzNSOzCsHrNH- -OC|;H4CH20H=CH1 NHCaH4CnH4S0aH /CH2 HgNSOzCoH4NH- N\ -NHCBH5SO3N3 (3) (A) (OzNa) Cl; +2NHr-aryl-S 311 aNs) (NH-aryl-S 0 3H wherein A and Y are as previously defined, (C N represents the 1,3,5-triazine ring, and aryl represents divalent aromatic nucleus. The reaction can be further generalized by the use of the reactant T--H wherein T is as previously defined and H is an active hydrogen atom attached to the T group, e.g.

1) (A);(0sNa)Gl+TH Momma or 2 (A)(C:Ns)Cl-2+2TH omem) (s) C;N3)(C1)+TH (C;N:)T

Some specific examples of the above reactions are ZNaOH NHKCuNiKNHCflHASOsNfl):

2Na0H (a) (UQN3)C1+NH2CLH4SO3H (CgNflNHCgHJSOzNB H0 Alternately, these compounds can be prepared by using a halotriazine containing an aryl sulfonic acid substituent 13 and reacting it with a compound containing a reactive hydrogen, represented by MH, wherein M represents Y or A groups as defined above, for example,

drohalide cycloh'exyl amine, etc., numerous examples of which are given in my copending application Serial No. 764,252, filed September 30, 1958.

The following "examples illustrate the practice of this invention and are given by way of illustration and not by limitation. Parts and percentages recited herein, unless otherwise specified, are parts by weight and :Percent by weight.

Example I In a-suitable reactor-equipped with a 'stirrerand reflux "condenser, there --is added 1455 parts of 2,4-diamino-6- monochloro-1,3,5-triazine in 200 parts of water'and the mixture heated to and maintained at a slow reflux. There is added slowly over a period of an hour a mixture of '170 parts of the sodium salt of paraminobenzene-sulfonic acid and'40 parts of NaOI-I in 230 parts of water. The reaction is continued for -8 hours, after which the mixture is allowed to cool to room temperature. There is obtained an almost quantitative yield of Upon the addition of 49-50 parts of H so, to the above solution; there isobtained' the free triazinylsulfonic acid derivative of the formula mnnzt iN's) KNHCSHt B which, after drying, gives on analyses 29.5% nitrogen,

3.51% hydrogen, 37.46% carbon, 11.63% sulfur, and a molecular weight of 282.2, which values are in close agreement with the theoretical. V

When 165 parts of the monoamino-dichlorotriazine are reacted instead of the monochlorotriazine with 340 parts of'the sodium salts of para-amino-sulfonic acid and 80 parts of NaOH, there is obtained which on analysesgives-values of 19l0% nitrogen, 3.21%

hydrogen, 41.06% carb'on,'14.42'% sulfur, and a" molecularweight" of 436.7, which values are in closeagreement with the theoretical values. 7

When the other halotriaiiiiesof the formula )z( s a) L Or a a)( z),

cannot are used instead of the specific monoand dihalotriazines of the paper. 'acid form can'be used for the separation and identification rap'hy techniques.

of this example, then, the corresponding derivative is obtained. Likewise when other sulfonic acids corresponding to the formula T-H are used, then the corresponding sulfonic acid derivatives are obtained. In a similar manner the triazino-halogeno-compounds of the formula (T) (C N )Cl and (T) (C N )Cl are used to prepare the triazine derivatives of this example.

Example 11 g Parts (NH (C N )NHC H SO H 140 Aqueous CH O (37.5%) NaOH in parts H 0 20 are heated together under'reflux at the boiling point of the mixture for 30-45 minutes yielding a'viscous resinous dis persion which can be used directly as a tanning agentas shown in later examples, either as prepared or diluted to the desired concentration of solids. Also, it'canbetreated with sulfuric acid to liberate the'resinous acid having free sulfonic group, which resin can be converted by heating to an insoluble, fusible product suitable 'as an ion exchange resin. Alternately, the sodium can be converted to other salts such as the calcium, copper, antimony, nickel, etc. by the addition ofan aqueous solution of such a salt, e.g., copper sulfate, cupric chloride, ferrous acetate, etc. These metallated resins, e.g. the copper resinate, can be used with cellulosic fillers such as cotton, wood flour, alpha flock to prepare molding compounds which "are fungus and mold-resistant. They can also be used as coating and impregnants for wood as wood preservatives, especially the copper and arsenic salts.

The specific resin of this example, particularly in the form of the polyethylene-imine salt, can also be used to impregnate paper and other fibrous sheet material and thereafter cured by heating to increase the wet strength Paper impregnated with the resin in its of organic bases using the standard paper-chromatog- For these and other uses, this resin can be modifiedasshown in subsequent examples.

Example III 7 Parts NH (C N3)'(NHC H SO;4H) 442 Aqueous formaldehyde (37.5% CH O) -NaOH in 20 0"-parts H2O 80 'fonic groupsforieach triazine ring and therefore can be reacted in part with other metalssuch as copper and still 'fretain gooddispersibility in water "and related solvents.

'and'III alone, a'mixture of such'derivatives can .be'us'e'd to -producea wide variety of gondensation productsvary- Zing from one sulfonic group to two sulfonicgroups 'per triazine ring in the condensation iproduct.

Instead of using the triazine derivatives of Examplesl II Example "I V -In-a reaction flask equipped with a stirrer-.andreflux condenser are mixed 7 The mixture heated 'to 90 i C. "for 1 hour thereafter. is cast into a' shallow container and heated inan oven until "the product is dry and hard. Thepro'duct is thengroun'd,

washed-with distilled waterand redried. The-resulting acidic ion exchange resin absorbs about 89.91% of'the calculated amount of NaOH from a 5% NaOH solution and then" exchanges the sodium ion forcalcium, magne- 15 sium, copper, silver ions, etc., upon treatment respectively with solutions containing such ions.

This condensation product can be modified by cocondensing the triazine derivative and the aldehyde with other aldehyde reactable substances, including those that have ion exchange resin groups, e.g., urea, melamine, phenol, phenolsulfonic acid, etc. An amphoteric ion exchange resin is readily prepared by using a triazine having a multiplicity of groups having ion exchange properties, e.g., a triazine having both a sulfonic group and an amine p, -8" 2) s s) G 4 3 (NH-pyridyl) Example V Fifty pounds of pickled sheepskins are placed in a drum with 100 pounds of 5% salt solution and the drum is rotated. There is then added 39 pounds of the condensation product of Example II, three portions of 13 pounds each at one-half hour intervals, and the drumming continued for 6-8 hours. The skins are then allowed to lie in the liquor for 8-10 hours and then drummed for another one-half hour, after which the skins are drained and washed thoroughly, set out, crusted, and finished by the ordinary methods with excellent results. In a similar manner kid skins, pig skins, calf skins, snake skins, deer skins, bear skins, alligator skins, shark skins, etc., are tanned.

The tanning agents of this invention can also be used as a supplementary tannage, for example, for skins that have been given a preliminary chrome or alum tannage, or they can be used in conjunction with other natural or synthetic tannages, as for example:

A. Fifty pounds of chrome tanned kidskins at the end of tannage and before being dried out are added to 50 pounds of water in a rotating drum together with 8 pounds of the condensation product of Example II. The drumming is continued for 2 hours after which the skins are washed thoroughly, fat-liquored, set out, crusted, and finished by the ordinary finishing methods with excellent results.

Fifty pounds of alum tanned calfskins are given a supplementary, excellent tanning using 10 pounds of the condensation product of Example H, using the procedure used for tanned kidskins.

Instead of the condensation product of Example IL the condensation products of Examples VI to XVI inclusive, respectively, are also used in the above procedures to produce light colored tanned leather which shows high shrink temperatures.

Instead of using the condensation products alone, the products of this invention can be used with other natural and synthetic tanning agents for example, by using mixtures of liquid quebracho extract with the condensation products of this example. For example, 100 pounds of pickled pig-skins are treated with 40 pounds of a mixture of equal parts of liquid quebracho extract and the condensation product of Example II, in 300 pounds of a 5% salt solution in a rotating drum. Ten pounds of the tanning mixture are added in four equal feeds at intervals of about one-half hour and the drum continued for an additional 4-5 hours, after which the skins are allowed to remain in the liquor for 1-2 hours, then drummed for an additional hour. At the end of the drumming period, the hides are washed thoroughly, fatliquored, set out, crusted, and finished in the ordinary method with excellent results.

Instead of the quebracho extract used above, synthetic tanning agents can be used, such as the reaction products 1 5 acted for 2 hours, after which parts of water and 60 parts of 38% formaldehyde are added and the temperature maintained at -85 C. for one hour. The solution is then cooled, the excess sulfuric acid neutralized with sodium hydroxide, and then diluted with water to a 45-47% solids content for use in tanning mixtures containing the condensation products of this invention. Alternately, the aromatic sulfonic acid can be condensed with an aldehyde, for example, phenol sulfonic acid and formaldehyde, initially together with the triazine derivatives of this invention to produce tanning agents with improved color over corresponding aromatic-aldehyde compositions in which the triazine derivatives have been omitted, e.g.:

Ninety-four parts of phenol is heated to 35 C., 150 parts of 66 Baum sulfuric acid is added slowly, and the temperature raised to -1003 C. and maintained at this temperaure for 2 hours. Seventy parts of water are then added together with 15 parts of and 65 parts of 38% formaldehyde solution and the reaction continued for 2 hours. The solution is then cooled, the excess mineral acid neutralized with sodium hydroxide and the resulting solution diluted to the desired strength. This solution is used directly as a tanning agent as shown hereinabove.

Example VI Moles (NH (C N (NHC H SO H) 1.00 CH O (38%) 2.25

Butyl alcohol 30.00

after which the mixture is neutralized with ethanol amine, followed by dehydration to remove water and diluted to the desired concentration. When the triazine derivative is intercondensed with formaldehyde and a polyhydric alcohol, e.g. glycerine, sorbitol, etc., a water soluble condensation product is obtained which produces a softer tanned leather.

Example VII Parts 2)z( HC H SO I-I p-Toluene Sulfnnamirla 5 Aqueous CH O (37.5%) NaOH in 50 parts H O 17 The above ingredients are refluxed for one-half hour to produce a syrup which has a slow cure. The addition of acids, such as sulfuric, phthalic anhydride, or of curing agents, such as chloroacetamide accelerates the cure.

Example VIII Parts NH (C N )(NHC H SO H) 120 Aqueous CH O (37.5% CH O) 190 Phenol 30 To the above mixture is added sutficient 20% NaOH solution to adjust the pH to 8-8.5 and the mixture refluxed for 1-2 hours to produce the condensation product.

Example IX Parts Melamine 50 Aqueous CH O (37.5% CH O) 210 NaOH in 10 parts H O 2 The above mixture is refluxed for thirty minutes and cures slowly on the hot plate at 120 C., but when 5 parts Of NH;;(C3N3) are added to the 17 syrup, a very rapid cure is obtained whereby the triazine derivative is intercondensed with the melamine-aldehyde reaction product.

NaOH in 10 parts H O 0.6

are refluxed together until a noticeable viscosity increase is observed. Then the mixture is cooled to room temperature and used with excellent results to impregnate soft-pine as a wood preservative.

Example XI Parts (NH (C N )OC H SO NH 120 Aqueous CH O (37.5% CH O) 210 NH;, (in 5 parts CH O) 1 Aqueous trimethylol melamine (50% solution) 130 When the above mixture is refluxed for 20-30 minutes, a syrup is obtained which cures alone when heated to 100-130 C. on a hot plate.

Example XII Parts (NH (C N )OC H.;,SO NH 120 Aqueous C11 0 (37.5% CH O) 150 Glycerine 20 are mixed and refluxed for 30 minutes and the condensation products are used directly in the tanning of hides after dilution to the desired concentration.

Example XIII Parts (NH C N NHC H SO K 12o Aqueous CH O (37.5% CH O) 140 Diethyl malonate- 20 NaOH in parts H O 0.2

are refluxed for minutes to produce a water-dilutable condensation product.

Example XIV Parts (NH C N NHC H SO Li 120 Aqueous CH O 140 NH (in 5 parts H O) 1 Acetamide 15 The above ingredients are refluxed for 15 minutes to produce a clear syrup suitable as an impregnating composition.

Example XV Parts (CH NH) C N NHC H SO K 60 Aqueous formaldehyde (37.5% CH O) 80 Polyvinyl alcohol (in 50 partsH O) 5 are refluxed for minutes to produce a clear syrup which can be used for tanning of hides or as a mordant for wool, silk, or cotton, and as an impregnant for paper, wood, etc.

are mixed together, refluxed for 10 minutes and then mixed with 30 parts of alpha flock, dried and molded at 130 C. to produce a hard, well-knit product.

1s Example XVII Parts Shellac 50 Calcium salt of product of Example I 15 are ground together and then heated together at 150 C. to produce ,a hard, infusible resin. This modified resin can be used as a mica binder.

Example'XVIII v n I Parts Alkyd resin (e.g. glyceryl phthalate) 50 Calcium salt of product of Example I' I 15 The components are mixed together and heated to C. and cures to a hard, infusible product which can be used as a mica binder.

The invention claimed is:

l. A composition of matter comprising the reaction product of a mass comprising an aldehyde and a triazine derivative having the formula:

wherein at least one of said valencies is attached to an aldehyde-reactable group and at least one of said valencies is attached to a group containing an aromatic homocyclic nucleus having substituted thereon 1 to 3 groups selected from the class consisting of sulfonic acid radicals and sulfonated radicals in which the hydrogen of the sulfonic acid radical is replaced by a member selected from the class consisting of a metal, ammonium radical and amino radical, said 'aldehyde being reacted in an amount of about 1-8 moles per mole of triazine derivative, and said reaction being conducted at a temperature of at least room temperature.

2. A composition of claim 1, in which said mass also comprises melamine.

3. A composition of claim 1, in which said mass also comprises dimethylol urea.

4. A composition of claim 1, in which said mass also comprises a glyceryl phthalate resin.

5. A composition of claim 1, in which said aldehyde comprises formaldehyde.

6. A condensation product of an aldehyde and 2) 2( 3 3) (NHC H SO H) 7. A condensation product of claim 6, in which said aldehyde is formaldehyde.

8. A condensation product of an aldehyde and NH (C N (NHC H SO H) 2 9. A condensation product of claim 8, in which said aldehyde is formaldehyde.

10. A condensation product of an aldehyde and (CH NH--) C N -O C H SO H 11. A condensation product of an aldehyde and NH -C3N3NHC5H3(SO3H)2 12. A process for preparing resinous products comprising the step of reacting an aldehyde with a triazine derivative having the formula:

wherein at least one of said valencies is attached to an aldehyde-reactable group and at least one of said valencies is attached to a group containing an aromatic homocyclic nucleus having substituted thereon 1 to 3 groups selected from the class consisting of sulionic acid radicals and sulfonated radicals in which the hydrogen of the sulfonic acid radicals is replaced by a member selected from the class consisting of a metal, ammonium radical and amino radical, said aldehyde being rected in an amount of about 1-8 moles per mole of triazine derivative, said reaction being conducted at a temperature of at least room temperature, and being catalyzed by an agent selected from the class consisting of alkaline and acidic aldehyde-condensation catalysts.

13. A process of claim 12, in which said aldehyde is formaldehyde.

a a 7 2i) 14. A process of claim 13, in which said reaction is performed in a mixture also containing another aldehyde reactable compound in addition to said triazine derivative.

15. A process of claim 14, in which said other aldehyde-reactable compound is melamine.

16. A process of claim 14, in which said other aldehyde-reactable compound is dimethylol urea.

References Cited in the file of this patent UNITED STATES PATENTS 2,643,990 Ham June 30, 1953 

1. A COMPOSITION OF MATTER COMPRISING THE REACTION PRODUCT OF A MASS COMPRISING AN ALDEHYDE AND A TRIAZINE DERIVATIVE HAVING THE FORMULA; 